Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



nited States Patent 2,781,378 Patented Feb. 12, 1957 DETERGENT SULPHONIC ACID AND SUL- PHATE SALTS OF CERTAIN AMPHOTERIC DETERGENTS No Drawing. Application December 21, 1955,

Serial No. 554,424

7 Claims. (Cl. 260-401) This invention relates to novel compositions and to methods for producing them. In one of its more specific aspects, the invention is directed to the method of making and to novel derivates of metal salts of substituted amido, amino acids, to which I shall hereinafter refer to as amino acid metal salts.

Said amino acid metal salts have been found useful as detergent, foaming, wetting, emulgating, emulsifying and dispersing agents. They are surface active agents, and serve as excellent synthetic detergents, dye assistants and softeners in the textile and related fields.

Said amino acid metal salts, employed as starting materials in the practice of this invention, have the following general Formula 1:

Rz-COOM in which R is an organic radical, which, if connected to a carboxyl group, provides a monocarboxylic acid, and said radical contains at least 4 carbon atoms and for most purposes is a hydrocarbon radical of 4-18 carbon atoms; R1

is hydrogen or an aliphatic hydrocarbon radical having 1-4 carbon atoms, such as CH3, C2H5, C3H7, and -C4H9 or any one of said radicals having one or more of the hydrogens thereof which has been hydroxy substituted, illustrative examples of which are or any one :of said radicals, but of 2-4 carbon atoms and Whose hydrogens have been either unsubstituted or hydroxy substituted and having a single ether (O) or keto (-CO-) linkage therein, illustrative examples of which are -C; .H4OCH3, -C2H4OC2H4OI-I, CHzCI-IOH O CzHs, CH2 CO CH3, -C2H4CO-C2H4OH, CH2OH--CO-C2H5; R2 is a hydrocarbon group having 1-4 carbon atoms, such as -CH2-, C2Ht-, -CaHs and --C4Hs, or any one of the aforesaid groups, any one or more of whose hydrogens has been hydroxy substituted, illustrative examples of which are -CH2CHOHCH2-,

CH2CHOHCHOHCHa-, I

Said amino acid metal salts may be produced in a number of ditferent Ways:

One of the methods which may be employed is to first react an hydroxy diamine with an organic acid in the molecular proportion of 1 to 1. When approximately 1 mol proportion of water of reaction has been formed and the acid number of the mass is zero, the reaction is terminated, and the resulting reaction mass under specific and controlled conditions is reacted with a metal salt of a monohalomonocarboxylic acid to provide an amino acid metal salt defined in Formula I.

The organic acid reacted with said diamine is one containing a single COOH group or any of the available anhydrides of said acids and by the term monocarboxylic organic acid as used herein, I mean to include both the acid and the anhydride thereof which I regard as the equivalent of the acid. These acids may be: the aliphatic :open chain saturated or unsaturated fatty acids as well as said fatty acids containing hydroxy or keto groups and/ or other substituents, such as aryl radicals, as for example, acids of the type of Twitchell fatty acids; cycloaliphatic carboxylic acids preferably containing no more than 4' at least 5 carbon atoms and preferably 5-19 carbon atoms in straight chain relationship. The acids which I employ may be derived from a number of different sources. Among some of them are the acid components chosen from oil or fats of animal, marine or vegetable origin and these include; the acids of cocoanut, palm kernel and palm oil, also from soy bean, linseed olive, rapeseed, cottonseed, peanut and castor oil which contain large proportions of unsaturated hydroxy fatty acids and also the acids derived from tallow, fish and seal oils, whale or shark oils and the hydrogenated acids from these sources. Moreover, the synthetic high molecular weight fatty acids, obtained by the oxidation of paratfin wax and similar high molecular weight hydrocarbons by means of gaseous oxidizing agents may be employed. In addition the acid may be one of the resinic acids, such as abietic acid, or the naphthenic acids and long chain fatty acids having an aromatic hydrocarbon radical connected directly with the aliphatic chain (Twitchell fatty acids) as are obtainable from oleic, ricinoleic, linoleic and similar unsaturated fatty acids. Instead of employing mixtures of acids from oil, fats and resins, single acids may be used, for example, caproic, myristic, heptylic, caprylic, undecylic, lauric, palmitic, stearic, behenic, arachic, cerotic, oleic, erucic, linoleic, linolenic, ricinoleic and hydroxystearic acids.

Of the aforesaid diamines I prefer to employ aminoethylethanolamine hereinafter referred to as reactant A. Because it is commercially available in large quantities, its use provides for etficient production of some of the starting materials.

Examples of some of the other diamines which may be employed in the production of starting materials are methyl amino isopropyl isopropanol amine (CHsNI-ICaI-IsNI-ICsI-IcOI-I),

amino isobutyl isobutanol amine (NH2C4H8NHC4H8OH), amino hydroxypropyl propane diol amine propyl amino ethoxy ethyl ethoxy ethanol amine (cmquuczmocrumncniiocanton butyl amino hydroxy propyl acetol amine (C4H9NHC3H5OHNHCH2COCH2OH) ethyl amino propanoneethanol amine (cgHsNHCHzCoCl-lzNHCzl-hOI-l) respectively, hereinafter referred to as reactants B, C, D, E, F and G.

The reactants AG respectively may be produced by employing a number of different classical methods well known to the art. One method consists essentially in reacting ammonia with a compound which is the dichloride of the R2 group between the two nitrogens and has formula ClR2-Cl, and subsequently treating the diamine produced with caustic soda to remove HCl which is attached. Then the resultant diamine is reacted with a compound of the formula Cl--R2-OH, and if R1 is other than hydrogen, another reactant Ri-Cl is used. Again, the hydrochloride is removed. In this mannor, the various diamines employed in the production of my starting materials may be produced and are of the following formula:

in which R1 and R2 have heretofore been defined.

One of the Well-known commercial methods employed in the production of said diamines whose general formula is above set forth is predicated upon the reaction of epoxy compounds, such as, ethylene oxide, propylene oxide, etc., with ammonia to form the intermediate diamine which is subsequently reacted with additional epoxy compound in the presence of water.

Among some of the salts of the halo acids which may be employed are the sodium and potassium salts of monochloracetic acid, monochlorpropionic acid, monochlorlactic' acid, monochlorhydroxyacetic acid, obtainable from di-chloracetic acid, monochloracetoacetic acid, monochlorethoxyacetic acid, etc.

One of the general types of method which may be employed for the production of some of these starting materials consists in first reacting one mol of a monocarboxylic acid having at least 4 carbon atoms in its radical connected to its COOH group with one mol of one of said diamines, examples of which are reactants AF, until onlyapproximately 1 mol of water has been removed. In carrying out this reaction the mixture is first heated to about 110180 C. in vacuum of 90-130 mm. of mercury pressure until one mol of water of reaction has been produced and removed. (All of the terms mm. and mm. pressure" as used in this entire description are intended to mean mm. of mercury pressure.) The reaction mass is then allowed to cool to room temperature and is then at elevated temperatures reacted with a monohalocarbo-xylic acid in the presence of 2 mols of caustic soda in aqueous solution. In one of its preferred forms one mol of said reaction mass is added to an aqueous solution containing one mol of the monohalocarboxylic and 2 mols of caustic soda, which solution prior to the addition has been prepared and maintained at a temperature no greater than 20 C. The mix is heated to a temperature of 95 C. until the pH has been reduced from about 13 to 88.5 and there is no further change in pH upon continued heating at said temperature.

Another ymethod which may be employed for producing starting materials of Formula I in the practice of this invention is as follows:

The reaction mass of the monocarboxylic acid and the dia-inine, an example of which is product X, is heated to 90l00 C. and there is gradually added thereto an equi-molecular proportion of monohalomonocarboxylic acld, such as monochloracetic acid, whereupon exothermic reaction occurs and the temperature rises from 90-100 C. to about 130-460 C. The resultant is allowed to cool to 100'C. and is then dissolved in water. To

this solution is added an aqueous solution containing 2 mols of caustic soda for each mol of monochloracetic acid previously used. This mass is stirred for about 15 minutes at a temperature of about 60 C. The resultant product is a reaction product as defined in Formula I.

Still another method which may be employed for the production of the intermediate, known herein as product X, is to react an acid chloride, having. the general formula R-CO-Cl, R being heretofore defined, with the diarnine'in the presence of water and caustic soda.

The following are illustrative examples given merely for the purposes of specifically illustrating how some of the starting materials employed in the practice of the present invention may be produced, all parts being given by weight unless otherwise specified.

EXAMPLE A 200 parts of lauric acid and 104 parts of reactant A are placed in a reacting vessel and are heated sufiiciently to melt the lauric acid whereupon an agitator located therein is started and mixes and maintains these components in mixed condition. While being constantly agitated the mix is heated under vacuum of about 110 mm. pressure for about 3 hours while gradually raising the temperature to 170 C. During this period 18 parts of water have been formed and distilled off, leaving behind a reaction mass having an acid number of approximately zero. Then this reaction mass, herein known as product X, is allowed to cool to room temperature and the entire mass is added to a previously prepared solution produced by adding 96 parts of monochloracetic acid and parts of caustic soda to 300 parts of water. This solution was prepared and maintained at a temperature below 20 C. before the addition of said reaction mass. This mixture is heated to C. and maintained at this temperature for 2 hours. During this period the pH of the mix is reduced from approximately 13 to 88.5. At the end of this period the pH of this mass is no longer subject to change by continued heating at said temperature and a sample of the resulting product is water soluble to a sparkling clear solution. At the end of this period the mass consists chiefly of a water solution of one of my starting materials, hereinafter known as product A and having the following formula:

EXAMPLE B To the aqueous mass produced under the method of Example A and containing 389 parts of my product A, whose formula is defined therein, there is added an aqueous solution consisting of 40 parts of caustic soda dissolved in 40 parts of water. Then to said mixture there are added 80.5 parts of chlorhydrin. This mixture which at this stage is at roomtemperature is heated over a period of 1 hour to 95 C. The mass is subsequently maintained at this temperature of 95 C. until there is no change in pH, this taking approximately 2 to 3 hours. The reaction mass consists essentially of an aqueous solution of another one of my starting materials, hereinafter known as product B, and having the formula which is the same as that of Example A, except that C2H4O'C2H4OH is substituted for Calla-OH.

EXAMPLE c .300 parts of water prepared and maintained below 20 C.

The resulting mixture isthen heated under the same conditions as outlined in Example A until the resulting product forms sparkling clear aqueous solutions and is no longer subject to pH change in continued heating. At the end of this period of the mass consists chiefly of an aqueous solution of one of my starting materials, hereinafter known as product C, and having the formula the same as that of Example A, except that C9H19 is substituted for CnHzs and C2H4COONa for the CH2COONa therein.

EXAMPLE D 282 parts linseed fatty acid and 104 parts reactant A are treated in the same manner as described in Example A. The entire reaction mass is then processed with an aqueous solution of 96 parts monochloracetic acid and 80 parts of caustic soda previously made and maintained below 20 C. and subsequently processed in the manner of Example A to produce starting material, hereinafter known as product D, and having the same formula as that of Example A except that C17H31 is substituted for C11H33 therein.

EXAMPLE E 116 parts of caproic acid and 104 parts of reactant A are condensed in the manner as described in the previous examples and the resulting reaction mass is subsequently processed in the same manner as that set forth in the processing of that of Example A.

The reaction product has the same formula as that of Example A, except that C5H11 is substituted for C11H23 therein, and is hereinafter known as product E.

EXAMPLE F EXAMPLE G 290 parts dodecyl benzoic acid and 104 parts of reactant A are condensed in the manner described in Example D and the resultant mass is processed in the manner of Example D, whereby there is produced a novel compound having the same formula as that of Example A, except that C12H25CsI-I4 is substituted for C11H23 therein, and is hereinafter known as product G.

EXAMPLE H 228 parts of myristic acid and 104 parts reactant A are reacted in the manner described in Example D and the resultant mass is processed in the manner of Example D, whereby there is produced a starting material hereinafter known as product H, and having the same formula as that of Example A, except that C13H27 is substituted for CnHzs therein.

Still another type of methods may be employed to produce some of these compounds, and examples thereof are shown hereinafter merely in an illustrative and not in a limiting sense.

EXAMPLE I 1 mol of lauric fatty acid and 1 mol of ethylenediamine (NHzCzi-LrNl-lz) are added together and then heated in the presence of an inert solvent such as toluol in amounts sutficient to dissolve the same. This solution is maintained at a temperature of approximately 110 C. This heating is carried out under a condenser through which pass vapors which consist of some of the solvent and water of reaction as well as small amounts of unreacted amine. These products are caught in a collector from which the water of reaction is removed and the condensed toluol and collected amine are returned to the reacting vessel. The temperature of the mass is maintained at 110 C. under the aforesaid conditions until 0.9 mol of water is collected. Then a vacuum of approximately mm. of mercury is applied to the reacting vessel and the temperature maintained at C. until all of the solvent and an additional 0.1 mol of water have been removed. To the resulting mass is added 1 mol of monochloracetic acid and this mixture is heated to a temperature of approximately C., whereupon the temperature of the mass will spontaneously rise to C. By the application of external heat the mass is maintained at said temperature at approximately 170 C. until a one part sample thereof when dissolved in 100 parts of aqueous solution of sodium hydroxide having a pH of approximately 9 provides a clear solution. 1 mol of this mass'so produced is added to an aqueous solution containing 1 mol of sodium hydroxide. The entire mass is heated to approximately 80 C. whereupon there is formed the sodium salt of said mass, having the following formula:

The aforesaid salt, whose structural formula is shown in this example may be produced instill another way. Instead of adding the monochloracetic acid at the stage previously shown, there first may be prepared an aqueous solution containing 2 mols of sodium hydroxide and one mol of monochloracetic acid. The temperature of this solution is reduced below 15 C. and preferably 5 to 10 C. and while maintained at said reduced temperature and being constantly agitated there is added thereto one mol of the lauric acid-ethylene diamine reaction mass. While being constantly agitated, the temperature of the mass is raised over a one-hour period to about 95 C. Then the temperature of this constantly agitated mass is maintained at 95 C. for an additional 3 hours or until a sample thereof in 100 parts of water will be clear and the pH is no longer subject to change on further heating of the mass at that temperature.

1 mol of the last defined compound is added to a solution containing one mol of caustic soda and one mol of chlorhydrin dissolved in water at a temperature not exceeding 15 C. and preferably between 5 to 10 C. After the addition at sa d low temperature, the mass is continuously agitated and while in the state of agitation its temperature is raised over about a one-hour period to 95 C. and is further continuously agitated and maintained at said temperature for an additional 3 hours, all of this being done under a reflux condenser. During said 3 hour period, the pH of the mass continuously decreases. At the expiration of that 4 hour period the pH of 1 part of the mass when dissolved in 100 parts of water will be 8.5. The 1 part sample when dissolved in 100 parts of water and having a pH of 8.5 in the water, provides a clear solution and is the same product as that of Example A.

EXAMPLE K By following the same procedureas that set forth in Example I with the only difference being that one mol of glycerine chlorhydrin(CH2C1-CHOH -CHz-OH) is substituted for the mol of ethylene chlorhydrin there is produced another one of my starting'materials, hereinafterknown as product K, and having a formula the same as that of Example A, except that CHzCHOHCHzOI-I is substituted for C2H4OH of Example A.

EXAMPLE L By following the same procedure as that set forth in Example I with the only difference being that one mol of pentaerythritol chlorhydrin (CH2.ClC(CHzOH)s) is substituted for the mol of ethylene chlorhydrin there is pro- '7 duced another oneof my starting materials, hereinafter known as Product L and having a formula the same as that ofExample A, except that -CH2C CHaOH) 20H is substituted for -a- CzH4OH of Example A.

EXAMPLE M By following the same procedure as that set forth in Example I with the only difference being that one mol of dimethylhydroxy ketone chlorhydrin (ClCH2COCHz-OH) is employed instead of the one mol of ethylene chlorhydrin there is produced another one of my starting materials, hereinafter known as product M, and having a formula the same as that of Example A, except that CHQCOCHZOH is substituted for CZHlOH of Example A. The ketone employed in this example may be prepared by employing the well-known method consisting essentially of the distillation of 2 mols of hydroxy acetic acid with one mol of calcium carbonate after which the ketone is chlorinated to provide the above reactant.

EXAMPLE N By' following the same procedure as that set forth in Example I with the only difference being that, instead of employing one mol of ethylene chlorhydrin, there is employed one mol of the following compound:

/OH GIOHgCOCH there is produced another one of my starting materials, hereinafter known as product N, and having the same formula as that of Example A, except that CHzCOCI-IOHOH is substituted for C2H4OH of Example A. The particular ketone reactant employed in this example may be produced by the'distiliation of one mol of dihydroxy acetic acid, one mol of hydroxy acetic acid and one mol of calcium carbonate after which the distillation product is chlorinated.

EXAMPLE P By following the same procedure as that set forth in Example I with the only difference being that one mol of monochlorlactic acid is employed instead of the one mol of monochloracetic acid so that there is produced still another of my starting materials, hereinafter known as product P, having the same formula as that of Example A, except that CHzCHOHCOONa is substituted for CHzCOONa of Example A. In this:

EXAMPLE, R

' Employing the same procedure as that set forth in Example A, except that 1 mol of stearic acid, 1'mol of reactant C and 1 mol of monochlorlactic acid are employed in place of the lauric acid, reactant A and monochloracetic acid, there is provided a starting material, hereinafter known as product R, having the following formula:

I CH3 OHzOHOHCOON-a EXAMPLE S Employing the same procedure as that set forth in Example A, except that 1 mol of myristic acid, 1 mol of reactant D and 2 mols of potassium hydroxide are used in place of the lauric acid, reactant A and caustic soda are used to provide starting material, hereinafter known as product S, having the following formula:

GHQ-4300K EXAMPLE T Employing the same procedure as that set forth in Example A, except that 1 mol of capric acid, 1 mol of reactant E, and 1 mol of monochlorethoxyacetic acid are used in place of the lauric acid, reactant A and mono- CHsCO GHz-C 0 ONE EXAMPLE V Employing the same procedure as that set fo1th in Example A, except that in place of the lauric acid, reactant A and caustic soda,'substitute 1 mol of dodecylbenzenemonocarboxylic acid (C12Hz5--C ;H4COOH), '1 mol of reactant G and 2 mols of potassium hydroxide, to provide starting material, hereinafter known as product V, having the following formula:

The specific monocarboxylic acids, as well as the specific monohalomonocarboxylic acids employed in certain examples, may be replaced by others as may be the variousother reactants in the specific examples to provide a great number of other starting materials, which differ from those set forth in the examples heretofore set forth.

Prior to this invention, it was known that cationic surface active agents and anionic surface active agents when together in aqueous solution resulted in the production or formation of water insoluble compounds; and that adding an anionic surface active agent to an aqueous solution of another anionic surface active agent resulted in a mere a'rsns'rs physical combination! of said agents and that no reaction would occur between them.

Said amino acid metal salts normally behave anionically in aqueous solutions having a pH above 7, and consequently it was expected that said amino acid metal salts" when in aqueous solution together with anionic surface agents that they would be combined physically only and that no chemical reaction would occur therebetween. In the course of my experimentations, I have discovered that said amino acid metal salts could be reacted with certain anionic surface active agents at a pH above 7 to produce Water-soluble reaction products. Not only did I make said discovery, but I further discovered that water solutions of such reaction products had viscosities greater than corresponding aqueous solutions of the amino acid metal salts and also exhibited better foaming characteristics than did said amino acid metal salts in very low dilutions under extreme water hardness conditions. Said reaction products are nontoxic and non-irritating to the human skin. They have been found eminently useful as general utility detergents, such as for car Washing, dish washing, clothes washing, etc. Said amino acid metal salts when used as components of shampoos sometimes caused slight irritation or stinging of the eyes when such shampoos were used and water solutions thereof accidentally reached the eyes. I have further discovered that the reaction products of this invention caused practically no irritation or stinging of the eyes when so employed.

According to this invention, one or a combination of two or more of said amino acid metal salts of the general structural Formula I are reacted with one or a combination of two or more anionic surface active agents of the following general structural Formula II to provide novel, water-soluble compounds having the following general structural Formula III, and having high wetting, detergency and surface active properties and capable of providing volumious and stable foams in aqueous solutions, and which aqueous solutions are substantially nonirritating to the skin and eyes of normal human beings.

Formula 11 Rs R- g-l q-R4XM Formula III R1 R2-OH R-COI l-R2N 0 R3 H R-("3NR4X wherein R3 is selected from the group consisting of (g) hydrogen, (h) aliphatic hydrocarbon radicals of l-8 carbon atoms, (1') hydroxy substituted aliphatic hydrocarbon radicals of 1-8 carbon atoms, (j) aliphatic radicals, each of said radicals having at least one ether linkage (O) therein and otherwise being hydrocarbon of 2-8 carbon atoms, (k) aliphatic radicals, each of said radicals having at least one ether linkage (O) therein and otherwise being hydroxy substituted hydrocarbon of 2-8 carbon atoms, (1) aliphatic radicals, each of said radicals having a keto linkage (-CO-) therein and otherwise being hydrocarbon of 2-8 carbon atoms, (m) aliphatic radicals, each of said radicals having a keto linkage (CO) therein and otherwise being hydroxy substituted hydrocarbon of 2-8 carbon atoms; R; is selected from the group consisting of (n) aliphatic, aromatic, and aromatic aliphatic hydrocarbon groups of 1-12 carbon atoms, (0) hydroxy substituted aliphatic, aromatic, and aromatic aliphatic hydrocarbon groups of l-12 carbon atoms, (p) aliphatic, aromatic and aromatic-aliphatic groups having at least one ether linkage (--O) therein and otherwise being hydrocarbon of 2-12 carbonatoms, (q) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups having at least one ether (O) linkage therein Ra-COOM l 10 and otherwise being hydr'oxy substituted hydrocarbon of 2-12 carbon atoms, (r) aliphatic, aromatic and aromaticaliphatic groups, each of said groups having a keto linkage (-CO) therein and otherwise being hydrocarbon of 2]2 carbon atoms, (s) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups having a keto linkage (-CO) therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, (t) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups including (CONH) and otherwise being hydrocarbon of 2-l2 carbon atoms, (u) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups including a --CONH- linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms; X is selected from the group consisting of (S03) and (0-303); and M is an alkali metal, preferably sodium or potassium, R, R1, and Re have been hereinbefore According to this invention, I react a compound of Formula I with a compound of Formula II to provide the novel and highly useful compounds of Formula III. In general this reaction is carried out in a solution containing compounds I and II and to which a quantity of an acidic agent such as a strong mineral acid, as for example hydrochloric, sulphuric or its equivalent, has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approximately 200 F. In this reaction under the aforesaid conditions, the compounds of Formula III are produced, said compounds having high water solubility. Such compounds of Formula III have an unexpected extremely high water-solubility, while the corresponding salts of cationic compounds are waterinsoluble. The resultant aqueous solution can be used directly as a surface active agent, wetting agent or detergent for the purposes indicated for the amino acid metal salts. While the quantities of the compound of Formula I and compound of Formula II may be equimoflecular for good yield of compounds of Formula III, I may employ an excess of either, and in general the mole ratio of a compound of Formula I to compound of Formula II may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out an aspect of this invention is to first dissolve a compound of Formula I in water and then the pH thereof is adjusted to approximately 12-13 (measured electrically) by the addition of aqueous caustic soda if required so that when a compound of Formula II is added thereto, the pH of the solution of I and II will be at least 10 and generally 10.5-11. The temperature of said solution is raised to l00200 F. and preferably in factory practice to approximately F Then a quantity of a compound of Formula II is dissolved in water in a separate container and this solution is added to said first solution and the mass is maintained in said temperature range while being constantly stirred, and an acidic agent is added thereto to reduce the pH thereof to a value below 10 and in the range of approximately 7 to 9, and preferably of approximately 8.2 to approximately 8.7. At the end of the acidic agent addition, the stirring is continued and the temperature of the mass maintained for about l020 minutes after which the solution is allowed to cool and is a finished product.

The following are specific examples merely given by way of illustrating the invention and are not to be taken by way of limitation, all parts being given by weight unless otherwise specified.

EXAMPLE 1 An aqueous solution of 400 parts of product A in 600 parts of water is heated to approximately 140 F. and its pH (measured electrically) is adjusted by the addition of aqueous caustic soda to 1213. While being constantly stirred and maintained at that temperature, there is added 2,781,537 8 a solution of 400 parts of s um salt of lauroylmonoj U OF NQVEL REACTION PRODUC'lf ethanolamide sulfate: 4 v H CQHPOH onun-co-rl -ona-hn o H CH2-COONa CuH23( (C2H O) SO3 in 600 parts of water. Then while stirring and the temperature is maintained there is added thereto between about -40 parts of hydrochloric acid solution (32%) EXAMPLE 6 whereby the pH of the mass is lowered to a value in the m 400 parts of product Q in 400 parts of water. 400parts range, of 82 t0 Stirring is continued and I116 of lauroylamidediethoxyetherethanolmouosulphate soperature maintained for about 10 minutes more. The di lt; resultant product is a solution of the novel react-ion prod O 62H) OQHMH elm-o H 1 5 I in 600 parts of water. C i1H23- C O-N- CgH l t FORMULA OF NOVEL REACTION PRODUCT O H H CH2 0 O ONa ii 1 CH3 CH3 CH2CH-OH EXAMPLE 2 O CzH' O C H OH H C2H4-C O O Na Employ the same procedure and components as set CH-C*N CZHOC2H* Os03 forth in Example 1 except that only about 200 parts of the sodium salt of lauroylmonoethanolamide sulfate are EXAMPLE 7 used. In this instance, the resultant product is a solution 550 parts of pwduct R in 850 parts of Water 400 Parts of the novel reaction product whose structural formula t of lauro l amidoeth lamidoacet lsu a l 1s shown in Example 1 together with unrea-cted product y y y lph te Qodwm Sat A used, in the approximate proportion of two parts of the I former to one ofthe latter. CuH2aCNC2HiNHCo CH2-SOa-N Employ the same procedure as that set forth in Ex- 600 parts of Watsr' ample 1, but employ the components indicated in the v Y 7 m p f following Examples 3-27; the quantity of hydrochloric FORMULA REALUUA PRODUC'l acid solution (32%) is variable to lower the pH to values C(CHQ)HCHZOH indicated in Example 1 to obtain the novel reaction prod- I v [55 C11Hs5-GON-O(CH:1)2CH2N ucts of said Examples 3-27.

EXAl P E (a I! CH2CHOHCOONa VI L 3 C11H23CN-CgH NHC O CHz-SO: 400 parts of product A in 600 parts of water. 400 parts of lauroyltaurate sodium salt: 40 EXAMPLE 8 0 CH H I 3 450 parts of product S In 500 parts of water. 300 parts C11Hfl1CN-C2H-1"SO3M1 of lauroyl sulfanilamide potassium salt:

in 600 parts of water. 3 I

FORMULA OF NOVEL REACTION PRODUCT r15 CuH2a( JN CuH4-SOsK OEH4 QH dissolved in 450 parts of water. T FORMULA OF NOVEL REACTION PRODUCT 0 OH; H GHQ-000m CHQCHOHCHQOH CHH,H (I L; 1\IT CZHQ SO3 CuHz7--CON-CH-;CHOHCHN (I? list H CH2 0 0 OK EXAIVIPLE 4 a v uH2a-CNCaH4-SOa 400 parts of product A in 690 parts of water. 450 parts of oleyldiethanolamide sulfate sodium salt: EXAMPLE 9:

o CZH-JOH 450 parts'of product T in 500 parts of water. 350 parts c H N of lauroyl amido methyl methyl phenyl sulfonate sodium salt; t V p 111 550 parts of water. 7 7 6O 1? E v T p 1 Y 1 Y I V FOLMUUt OB LOVEL REACTIOA VPRODUCL CUHH C N QH2 CaHr-OH 011111342 0-N-C2H4;-N\ 7 e OH CH3 9 (33114011 H QH -COONa C b I )0 dissolved in 500 parts of water.

EXAMPLE 5 FORMULA OF NOVEL REACTION PRODUCT t (75117 (321340 CzHr'OH 400 parts of product A in 600 parts of water 400 parts i QH- ---CO-N-GHOCHT of lauroyltriethoxyetheramlde sulfate sodlum salt: B m 3 i 2 i A I E 011140 CH7-COON3 V C1lH2P"CNC/H2 S03 i1160pa rtsofwater. a a H 13 EXAMPLE 10 400 parts of product A in 600 parts of water. 350 parts of lauroyl amido ethoxy methyl ethyl sulfate sodium salt:

oimooHs !lHfl3' I l C2H4-'S Oa-I l'a in 600 parts of water.

FORMULA or NOVEL REACTION PRODUCT C2H4-OH CllHir-C Ol l CgH4-N o CzHrO CH H CHPCOONB,

OnHaa- N-C2H4-SO;::

EXAMPLE 11 450 parts of product T in 500 parts of water. 450 parts of stearoyl amido propanone ethyl sulfate sodium salt:

0 CHa-OO-CHs C17H35 CNC2H4S O a-Na in 600 parts of water.

FORMULA OF NOVEL REACTION PRODUCT O CHg C2H4O CaH4-OH CuHrql }l TCzHAO CzHs-N o omoo 011i H oznloonwoooNa CuHar- N---C2Ht-'S0s EXAMPLE 12 550 parts of product U in 850 parts of water. 350 parts of lauroyl amido acetol ethyl sulfate-sodium salt:

CnH2a- CN C2H4-S O a-Na FORMULA OF NOVEL REACTION PRODUCT 04m c1120 0 CH -OH C11Ha -C0NCHzOH0HCHz-N 0 0112000111011 11 \CHQCOCHT-OOONQ- C11H:3 --N 02H; s04

EXAMPLE 13 550 parts of product U in 850 parts of water. 450 parts of myristol amido methyl glyceryl oxyethyl sulfate sodium salt:

0 CH3 C1SHZT- I q CH3CHOHCH2O C2H4OS03Na in 600 parts of water.

FORMULA OF NOVEL REAOTION PRODUCT 400 parts of product A in 600 parts of water. 300 parts of lauroyl amido acetol sulfate sodium salt:

550 parts of product V "in 800 parts of water. 300 parts of lauroyl amido propanone sulfate potassium salt:

OHz-C O ONa Employing the same procedure as that set forth in Example l, except that products B, K, L, M, and N are respectively substituted for product A to provide novel reaction products which differ from the novel reaction product whose formula is shown in Example 1, by substituting for the C2H4-OH radical thereof, the following respective radicals:

C2H4OC2H4OH, CI-IzCHOHCH2-OH CH2O(CH2OH)2-OH, CH2COCH2-OH CHzCOCHOH-OH EXAMPLES 21-24 Employing the same procedure as that set forth in Example 1, except that products D, E, G and H are respectively substituted for product A to provide novel reaction products, which differ from the novel reaction product whose formula is shown in Example 1, by substituting for the C11H23 radical thereof the following respective radicals:

C1'IH31, CsHn, C12H25C6H4 and C13H27 EXAMPLE 25 Employing the same pro cedure as that set forth in Example 1, except that product P is substituted for product A to provide a reaction product which difiers from the novel reaction product, whose formula is shown in Example 1, by substituting for the CHz-COONa radical the following radical: CH2-CHOH-COONa.

EXAMPLES 26 AND 27 Employing the same procedure as that set forth in Example 1, except that products C and F respectively are substituted for product A to provide novel reaction products which differ from the novel reaction product whose formula is shown in Example 1, by substituting C2H4-COONa for the CH2COONa and also substituting CsHrs and CmHas respectively for C11H23.

EXAMPLES 28-40 Employing the sameprocedure as that set forth in Example 3, except that, instead of product A, there are respectively substituted compounds which are the same 'as product A, except that the H of the NH attached directly to the CO group thereof is replaced by the following respective radicals:

menses pounds of Formula II employed in Examples 1-40, a great number of other novel reactionproducts whose formulas are that of Formula III may be produced; and in addition, the specific reactants employed may differ from those employed herein, in varying R, R1, R2, and R3 within the definitions thereof, to provide a great number of other compounds of Formula III.

It is to be understood that instead of first adjusting the'pH' of the compound of Formula I to 12-13 before the addition of the compound of Formula 11, any other method may be employed to obtain the condition whereby the pH of the solution of I and II is at least 10 and preferably 10.5-11 before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approximately 9. For example, I and II may be dissolved together and this solution may, by the addition of caustic soda when required, have its pH adjusted to at least 10, and then at IOU-200 F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution of pH of at least 10 is brought to a temperature in the range of 100-200 F.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

I claim: 1. A compound of the following formula:

R1 Rz-OH no 0-1h-Rr-N so Ra H m-OOOM ROI\ITR4X in which R is a hydrocarbon radical of 4 to 18 carbon atoms; R is an organic group selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms, (b) hydroxy substituted aliphatic hydrocarbon groups of 1-4 carbon atoms, (c) aliphatic other groups, each of said ether groups having an ether oxygen linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ether groups, each of said groups having an ether ogygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic keto groups, each of said groups having a carbonyl linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (f) aliphatic keto groups, each of said groups having a carbonyl linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms; R is selected from the group consisting of hydrogen and monovalent radicals otherwise defined in said (a)('f); R is selected from the group consisting of (g) hydrogen, (h) aliphatic hydrocarbon radicals of 1-8 carbon atoms, (i) hydroxy substituted aliphatic hydrocarbon radicals of l-S carbon atoms, (j) aliphatic radicals, each of said radicals having each of said groups having a carbonyl linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, (s) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups having a carbonyl linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, (1) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups including a -CONH-linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, (u) aliphatic, aromatic, and aromatic-aliphatic groups, each of said groups including a CONI -Ilinkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms; X is selected from the group consisting of (S0 and (0-80 and M is an alkali metal.

2. A compound of the following formula:

I C2H4OH R C O N- Calla-N o H H GH -000N9- R-h-fI-GrH-X in which R is a hydrocarbon radical of 4 to 18 carbon atoms, and X is selected from the group consisting of S03 and OSO3 3. A compound of the following formula:

(Jim-0H C n zr- 0 ()lil' CEHL-N C11Hzs C2H4-O-S O:

4. A c ompouud of the following formula: C 2114- O H CnHza-C O-lG-CrIL-N 0 OH; H OnHrF-( JI IC2 4S 0a 5. A compound of the following formula: CzHr-OH CH2COON8 CHr-COONa 6. A compound of the following formula:

arm-0H CHI-O O 0N9.

GHa-CO ONa 7. A compound of the following formula:

1?: CHaCH OHCHr-OH C13Hz7CO-NCH2CHOHCH5N I f) III H oHrOooK CnHza-C-NCsHr-SO: I References Cited in the file of this patent UNITED STATES PATENTS 2,103,872 Schoeller Dec. 28, 1937 2,329,406 Mauersberger Sept. 14, 1943 2,391,830 Jayne et'al. Dec. 25, 1945 OTHER REFERENCES 7' Sisley et ah: Encyclopedia of SurfaceActive Agents,

1952, pages 338, 470. 

1. A COMPOUND OF THE FOLLOWING FORMULA: 